2,7-dibromo-3,6-dimethoxy-9,9-dimethyl-9-silafluorene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,7-dibromo-3,6-dimethoxy-9,9-dimethyl-9-silafluorene
• 英文别名: 2,7-dibromo-3,6-dimethoxy-9,9-dimethylsilafluorene；3,7-dibromo-2,8-dimethoxy-5,5-dimethyl-5H-dibenzo[b,d]silole；3,7-Dibromo-2,8-dimethoxy-5,5-dimethylbenzo[b][1]benzosilole
• 化学式: C₁₆H₁₆Br₂O₂Si
• 分子量: 428.195
• InChiKey: RQWJEDZKGQSIED-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.03
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,7-dibromo-3,6-dimethoxy-9,9-dimethyl-9-silafluorene 在 哌啶 、 copper(l) iodide 、 四(三苯基膦)钯 作用下， 以 二氯甲烷 为溶剂， 反应 60.0h， 生成
  参考文献：
  名称：

  对称硅芴核心四氰基丁二烯和四氰基醌二甲烷衍生物的合成、结构和显着能隙调制

  摘要：

  设计了一系列具有 D-A-D'-A-D 结构构型和硅芴核 (D') 的对称四氰基丁二烯和四氰基醌二甲烷衍生物，并通过 [2+2] 环加成-逆电环化 (CA-RE) 反应轻松合成. 我们发现硅芴衍生物的光物理性质和 HOMO 和 LUMO 能级和间隙可以通过 CA-RE 反应进行深刻改造，并通过改变周边供体单元（从苯基、间二甲氧基苯基和N , N-二甲基苯胺到三苯胺）进行调节团体。CA-RE反应后， 1a-1j的HOMO-LUMO间隙在 1.75-2.78 eV 的范围内，与母体硅芴化合物2a-2j相比，显着降低了 0.52-1.46 eV 。分析和阐明了1f和1j的有趣晶体结构，以显示其独特的潜在孔隙率。系统地进行了稳定性、电化学和计算研究，以揭示一个分子系统中重塑的供电子和吸电子性质。1h–1j外周强氨基供体在 550 至 900 nm 的近红外区域表现出强烈而宽的分子内电荷转移吸收带。本文报道的分子设计和合成拓宽了

  DOI：

  10.1021/acs.joc.1c02382
• 作为产物：
  描述：

  联大茴香胺 在 potassium iodate 、 正丁基锂 、 硫酸 、 氢溴酸 、 碘 、 溶剂黄146 、 sodium nitrite 作用下， 以 四氢呋喃 、 正己烷 、 水 、 乙腈 为溶剂， 反应 25.5h， 生成 2,7-dibromo-3,6-dimethoxy-9,9-dimethyl-9-silafluorene
  参考文献：
  名称：

  Pure Blue Emitting Poly(3,6-dimethoxy-9,9-dialkylsilafluorenes) Prepared via Nickel-Catalyzed Cross-Coupling of Diarylmagnesate Monomers

  摘要：

  Polysilafluorenes (PSFs) are an important class of light-emitting conjugate polymers noted for their characteristic brilliant solid state blue luminescence, high quantum efficiency, excellent solubility, and improved thermal stability. These polymers are also reported to have superior electron conductivity to polyfluorenes. The higher electron affinity and conductivity, which are particularly promising for OLEDs, originate from sigma*-pi* conjugation between the sigma* antibonding orbital of the exocyclic Si-C bond and the pi* antibonding orbital of the butadiene fragment. In this paper, we present the synthesis and thorough characterization of several new derivatives of 2,7-dibromo-3,6-dimethoxy-9,9-dialkylsilafluorene monomers and demonstrate an efficient room temperature route to their polymerization. In addition to silafluorene monomers with simple alkyl side chains, we have increased the functionality of several of our monomers by incorporating vinyl, cyclohexenyl, and norbornenyl moieties into their side chains, which we believe is useful for postpolymerization modification. (i.e., adding pendant emitters to tune PL or cross-linking). The production of polymer was achieved using a nickel-catalyzed polycondenation of diarylmagnesate-type monomers in a mixed solvent system of THF and 1,4-dioxane (7:3). Using 1,4-dioxane as a cosolvent was discovered to significantly increase the Mg/Br exchange rate by a factor of 5, reducing the time required to achieve stiochiometric conversion of sterically hindered and electron rich 2,7-dibromo-3,6-dimethoxy-9,9-dialkylsilafluorene to 2 h. Also, relatively fast rates of polymerization were observed. Polymers reached their maximum molecular weight within 30 m. In many cases, M-n exceeds 50 kg/mol (PDI similar to 1.5-2.0). The resultant polymers possess characteristic blue photoluminescence with solid state quantum yields (exceeding 80% in many cases). Polymer films have excellent transparency (with a measured E-g similar to 3.0 eV) and thermal stability as demonstrated by TGA/DSC. Energy levels determined using CV were -5.62 and -2.62 eV for HOMO and LUMO, respectively.

  DOI：

  10.1021/ma401346y

文献信息

• Synthesis and photophysical properties of highly emissive compounds containing a dibenzosilole core
  作者：Liangchun Li、Caihong Xu、Shuhong Li

  DOI：10.1016/j.tetlet.2009.11.074

  日期：2010.1

  A series of new rigid rod-like molecules consisting of a dibenzosilole core, ethynylene linkages, and different aryl end-groups has been synthesized by palladium-catalyzed Sonogashira cross-coupling reactions. These compounds exhibit intense blue to green emissions with high quantum efficiencies and good thermal stabilities.

  通过钯催化的Sonogashira交叉偶联反应合成了一系列由二苯并甲硅烷基核，亚乙炔基键合和不同芳基端基组成的新型刚性棒状分子。这些化合物具有高量子效率和良好的热稳定性，显示出强烈的蓝绿色发射光。
• A General Strategy for the Facile Synthesis of 2,7-Dibromo-9-heterofluorenes
  作者：Run-Feng Chen、Qu-Li Fan、Chao Zheng、Wei Huang

  DOI：10.1021/ol0524499

  日期：2006.1.1

  A facile, highly efficient, and economical procedure for the preparation of 6,6 '-diiodo-4,4 '-dibromo-3,3 '-dimethoxylbiphenyl has been found. From this compound, a general synthetic strategy for the preparation of 2,7-dibromo-9-heterofluorenes has been developed. Five 2,7-dibromo-9-heterofluorenes have been easily synthesized for the first time according to the procedure presented, opening the door to new classes of inorganic and organometallic conjugated polymeric materials of polyheterofluorenes.
• The fluorescent liquid crystal and spiro-silicon bridged compounds based on silafluorene core
  作者：Ping Tang、Liangchun Li、Kai Xiang、Yanmin Li、Shuhong Li、Caihong Xu

  DOI：10.1016/j.jorganchem.2020.121178

  日期：2020.4

  Based on silafluorene core, the liquid crystal silafluorene and spiro-silicon bridged silafluorene compounds were synthesized. Apart from higher thermal stability, the obtained compounds containing liquid crystal units demonstrated liquid crystal behavior and fluorescent properties with higher solid fluorescent quantum yield. The spiro-silicon bridged compound displayed good solubility, which led to easy processing. Besides, it exhibited easy preparation and higher emissive fluorescent properties. (C) 2020 Elsevier B.V. All rights reserved.
• Pure Blue Emitting Poly(3,6-dimethoxy-9,9-dialkylsilafluorenes) Prepared via Nickel-Catalyzed Cross-Coupling of Diarylmagnesate Monomers
  作者：Jeffrey J. McDowell、Isabel Schick、Alastair Price、Daniel Faulkner、Geoffrey Ozin

  DOI：10.1021/ma401346y

  日期：2013.9.10

  Polysilafluorenes (PSFs) are an important class of light-emitting conjugate polymers noted for their characteristic brilliant solid state blue luminescence, high quantum efficiency, excellent solubility, and improved thermal stability. These polymers are also reported to have superior electron conductivity to polyfluorenes. The higher electron affinity and conductivity, which are particularly promising for OLEDs, originate from sigma*-pi* conjugation between the sigma* antibonding orbital of the exocyclic Si-C bond and the pi* antibonding orbital of the butadiene fragment. In this paper, we present the synthesis and thorough characterization of several new derivatives of 2,7-dibromo-3,6-dimethoxy-9,9-dialkylsilafluorene monomers and demonstrate an efficient room temperature route to their polymerization. In addition to silafluorene monomers with simple alkyl side chains, we have increased the functionality of several of our monomers by incorporating vinyl, cyclohexenyl, and norbornenyl moieties into their side chains, which we believe is useful for postpolymerization modification. (i.e., adding pendant emitters to tune PL or cross-linking). The production of polymer was achieved using a nickel-catalyzed polycondenation of diarylmagnesate-type monomers in a mixed solvent system of THF and 1,4-dioxane (7:3). Using 1,4-dioxane as a cosolvent was discovered to significantly increase the Mg/Br exchange rate by a factor of 5, reducing the time required to achieve stiochiometric conversion of sterically hindered and electron rich 2,7-dibromo-3,6-dimethoxy-9,9-dialkylsilafluorene to 2 h. Also, relatively fast rates of polymerization were observed. Polymers reached their maximum molecular weight within 30 m. In many cases, M-n exceeds 50 kg/mol (PDI similar to 1.5-2.0). The resultant polymers possess characteristic blue photoluminescence with solid state quantum yields (exceeding 80% in many cases). Polymer films have excellent transparency (with a measured E-g similar to 3.0 eV) and thermal stability as demonstrated by TGA/DSC. Energy levels determined using CV were -5.62 and -2.62 eV for HOMO and LUMO, respectively.
• Synthesis, Structure, and Significant Energy Gap Modulation of Symmetrical Silafluorene-Cored Tetracyanobutadiene and Tetracyanoquinodimethane Derivatives
  作者：Zhaoling Zhang、Gaozhang Gou、Jun Wan、Hui Li、Man Wang、Liangchun Li

  DOI：10.1021/acs.joc.1c02382

  日期：2022.3.4

  those of the parent silafluorene compounds 2a–2j. The intriguing crystal structures of 1f and 1j were analyzed and elucidated to show their unique potential porosity. The stability, electrochemical, and computational studies were systematically performed to unveil the reshaped electron-donating and -withdrawing nature in one molecular system. 1h–1j with peripherally strong amino donors exhibit an intense

  设计了一系列具有 D-A-D'-A-D 结构构型和硅芴核 (D') 的对称四氰基丁二烯和四氰基醌二甲烷衍生物，并通过 [2+2] 环加成-逆电环化 (CA-RE) 反应轻松合成. 我们发现硅芴衍生物的光物理性质和 HOMO 和 LUMO 能级和间隙可以通过 CA-RE 反应进行深刻改造，并通过改变周边供体单元（从苯基、间二甲氧基苯基和N , N-二甲基苯胺到三苯胺）进行调节团体。CA-RE反应后， 1a-1j的HOMO-LUMO间隙在 1.75-2.78 eV 的范围内，与母体硅芴化合物2a-2j相比，显着降低了 0.52-1.46 eV 。分析和阐明了1f和1j的有趣晶体结构，以显示其独特的潜在孔隙率。系统地进行了稳定性、电化学和计算研究，以揭示一个分子系统中重塑的供电子和吸电子性质。1h–1j外周强氨基供体在 550 至 900 nm 的近红外区域表现出强烈而宽的分子内电荷转移吸收带。本文报道的分子设计和合成拓宽了